DE69933094T2 - PHOTOCHROME POLYMERIZABLE COMPOSITION - Google Patents

Description

The The present invention relates to a photochromic polymerizable Composition containing a hardened Product with excellent photochromic effect results. Further concerns the invention is a photochromic material containing the photochromic polymerizable Composition contains.

photochromism is an apparition that in recent years is increasingly paying attention pushed is. It is a reversible effect in which the color a particular connection changes rapidly when the connection with light with a proportion of UV rays, as sunlight or light from a mercury lamp is irradiated, the compound returns to its original color when she is no longer irradiated with light and sent to a dark place is brought. A compound with such a nature is called a photochromic compound. Connections with different ones Colors have been synthesized so far, but with a problem in terms of durability the photochromism were connected when the compounds repeated the reversible change were suspended.

Therefore were photochromic compounds with improved resistance Photochromism developed, z. B. photochromic compounds from Oxazine type (hereinafter simply referred to as oxazine compound), Fulgimide-type photochromic compounds (hereinafter referred to simply as Fulgimidverbindungen called) and photochromic compounds of Chroma Type (hereinafter referred to simply as the chromene compound) (U.S. Patents 4,882 438, 4,960,678, 5,130,058, Japanese Kokai 288830/1987, U.S. Patent 5,106,998, Japanese Laid-Open (Kokai) 28154/1990, 11074/1991 and 133988/1991.

These Photochromic compounds have excellent resistance photochromism. In particular, the aforementioned chromene compounds become generally little affected by light. In continuous Irradiation with sunlight or light that comes close to sunlight, These chromene compounds only slightly lose their performance relative to on the color development and show excellent durability the photochromy.

Tries however, a photochromic material, e.g. B. photochromic lenses for glasses, by mixing the chromene compound with a polymerizable Monomers with the aim of polymerizing the materials, so occurs in the obtained photochromic material often a problem, although in the photochromic compound itself no special problems consist. A study carried out by the inventors revealed namely, that if a particular chromene compound as a photochromic Connection for a polyfunctional (meth) acrylate monomer, broadly as a monomer for producing a photochromic material, such as Eyeglass lenses, is used, it is not possible a photochromic material with good photochromic resistance and the photochromic material itself develops a color (often referred to as "initial color"). This poses a serious problem for the photochromic material, such as spectacle lenses, where strong the preference of the user arrives dar. Thus, there is a need to To provide photochromic material that has no initial color.

Around the durability the photochromism of the photochromic material containing to improve a chromene compound, WO 96/37576 describes Process in which a photostabilizer of the steric type hindered amino ether to a thermoplastic resin such as polyvinyl chloride or polycarbonate containing a benzochromium compound is given. The inventors have the aforementioned special chromene compound to the polyfunctional (meth) acrylate which, together with the aforementioned Photostabilizer of the sterically hindered aminoether type is marketed. However, the permanence of photochromism did not sufficiently improved and the development of the initial color could not be suppressed.

EP-A-0 875,509 (cited only under Article 54 (3) EPC) Compositions containing chromenes and certain polyfunctional ones (Meth) acrylate monomers, which are excluded here by a disclaimer become.

The Object of the present invention consists in the solution of Problems of initial color, which for the photochromic material is specific, which is cured by curing the Photochromic polymerizable composition containing a specific Chromene compound and a polyfunctional (meth) acrylate monomer contains is obtained, as well as in the solution the problem of reducing the permanence of photochromism.

The The present invention serves to achieve the aforementioned object and is based on the finding that a particular photochromic material has only a low initial color and a high resistance the photochromism shows, with this photochromic material by hardening a photochromic polymerizable composition is obtained, by adding an epoxy compound to the aforementioned photochromic polymerizable composition containing a certain chromene compound and a polyfunctional (meth) acrylate monomer is formed has been.

• a) ein polyfunktionales (Meth)acrylat-Monomer oder ein Gemisch oder ein Präpolymer von zwei oder mehr polyfunktionalen (Meth)acrylat-Monomeren,
• b) wenigstens eine Chromenverbindung der Formel (I),
  
  wobei R₁₆ eine substituierte oder unsubstituierte Aminogruppe oder eine Stickstoff enthaltende heterocyclische Gruppe ist, die als ein Heteroatom ein Stickstoffatom besitzt, das an einen Benzochromenring gebunden ist, wobei R17 und R18 gleich oder verschieden sein können und Alkylgruppen, Arylgruppen oder aromatische heterozyklische Gruppen sind, die einen Substituenten aufweisen können, und wobei R17 und R18 aneinander gebunden sein können, um einen Ring auszubilden, und
• c) eine Verbindung mit wenigstens einer oder mehreren Epoxygruppen in den Molekülen, unter der Maßgabe, dass das polyfunktionale (Meth)acrylatmonomer nicht nur besteht aus Ethylenglykoldiacrylat-Monomer, Diethylenglykoldimethacrylat-Monomer, Triethylenglykoldimethacrylat-Monomer, Tetraethylenglykoldimethacrylat-Monomer, Ethylenglykol-bis-glycidylmethacrylat-Monomer, Bisphenol A-Dimethacrylat-Monomer, 2,2-Bis-(4-methacryloxyethoxyphenyl)-propan-Monomer oder 2,2-Bis-(3,5-Dibrom-4-methacryloxyethoxyphenyl)-propan-Monomer oder einem Gemisch aus Tetraethylenglykoldimethacrylat und Triethylenglykoldimethacrylat.

Thus, the present invention relates to a photochromic polymerizable composition comprising:

• a) a polyfunctional (meth) acrylate monomer or a mixture or a prepolymer of two or more polyfunctional (meth) acrylate monomers,
• b) at least one chromene compound of the formula (I)
  
  wherein R _{16 is} a substituted or unsubstituted amino group or a nitrogen-containing heterocyclic group having, as a heteroatom, a nitrogen atom bonded to a benzochrome ring, wherein R 17 and R 18 may be the same or different and are alkyl groups, aryl groups or aromatic heterocyclic groups, which may have a substituent, and wherein R17 and R18 may be bonded together to form a ring, and
• c) a compound having at least one or more epoxy groups in the molecules, provided that the polyfunctional (meth) acrylate monomer is not only ethylene glycol diacrylate monomer, diethylene glycol dimethacrylate monomer, triethylene glycol dimethacrylate monomer, tetraethylene glycol dimethacrylate monomer, ethylene glycol bis-glycidyl methacrylate Monomer, bisphenol A dimethacrylate monomer, 2,2-bis (4-methacryloxyethoxyphenyl) -propane monomer or 2,2-bis (3,5-dibromo-4-methacryloxyethoxyphenyl) -propane monomer or a mixture from tetraethylene glycol dimethacrylate and triethylene glycol dimethacrylate.

The photochromic polymerizable composition of the present invention may further contain (d) a polymerization initiator.

Further The invention relates to a photochromic material comprising the aforementioned photochromic polymerizable composition.

The Photochromic according to the invention polymerizable composition gives a photochromic material, that in favorable Can be used as a spectacle lens that has a low initial color developed and has excellent resistance to photochromism.

Best embodiment to carry out the invention

Component (a)

below a polyfunctional (meth) acrylate monomer is described in it is the component (a) of the photochromic invention polymerizable composition.

Regarding of the invention used There are no specific polyfunctional (meth) acrylate monomers restrictions provided that there are two or more polymerizable groups, such as (meth) acryloyl groups, contained in the molecule and the disclaimer above considered is. A known polyfunctional (meth) acrylate monomer may be used which is widely used as a monomer for spectacle lenses becomes.

Specific examples of representative polyfunctional (meth) acrylate monomers which can be used alone according to the present invention include ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2,2-bis- (4- (meth) acryloyloxypolyethoxyphenyl) -propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) -propane, 2,2-bis- (4- (meth) acryloyloxypolypropoxyphenyl) -propane, an ester compound of di (meth) acrylic acid with a hydrogenated bisphenol A-ethylene oxide adduct, dimethylol tricyclodecane polyethoxydi (meth) acrylate, trimethylolpropane tri (meth) acrylate, a reaction product of polyethylene glycol with glycidyl (meth) acrylate, a reaction product of propylene glycol or polypropylene glycol with glycidyl (meth) acrylate, a reaction product of a bisphenol A-ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate and a reaction product of hydrogenated bisphenol A-ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate.

The polyfunctional (meth) acrylates may be in the mixture of two or more more species can be used or they can be in the form of an oligomer, used by prior partial polymerization become.

To concrete examples for representative polyfunctional (meth) acrylate monomers used in mixtures according to the invention or prepolymers can be used belong Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, Polypropylene glycol di (meth) acrylate, polybutylene di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 2,2'-bis- (4- (meth) acryloyloxyethoxyphenyl) -propane, 2,2'-bis (4- (meth) acryloyloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolypropoxyphenyl) propane, 2,2-bis (3,5-dibromo-4- (meth) acryloyloxyethoxyphenyl) propane, an ester compound of di (meth) acrylic acid with a hydrogenated bisphenol A-ethylene oxide adduct, dimethylol tricyclodecane polyethoxydi (meth) acrylate, Trimethylolpropane tri (meth) acrylate, a reaction product of ethylene glycol or polyethylene glycol with glycidyl (meth) acrylate, a reaction product propylene glycol or polypropylene glycol with glycidyl (meth) acrylate, a reaction product of a bisphenol A-ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate and a reaction product of hydrogenated bisphenol A-ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate.

In the photochromic invention The polymerizable composition may be a known one as needed Monomer as a copolymerizable monomer in addition to the above-mentioned polyfunctional (meth) acrylate monomer be given to the mechanical properties of the photochromic Material by hardening the polymerizable composition is obtained. For suitable examples of the copolymerizable monomer includes monofunctional (meth) acrylate monomers, such as methyl (meth) acrylate, Ethyl (meth) acrylate, butyl (meth) acrylate, isobornyl (meth) acrylate, Benzyl (meth) acrylate, phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, Phenoxypolyethylene glycol (meth) acrylate, alkoxypolyethylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate and tribromophenyl (meth) acrylate, polyvalent Allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl isophthalate, Diallyl tartrate, diallyl epoxysuccinate, diallyl fumarate, diallyl chlorendate, Diallylhexaphthalate, diallylcarbonate, allyl diglycolcarbonate and Trimethylolpropantriallylcarbonat; polyvalent thioacrylic acid compounds and Esters of polyfunctional thiomethacrylic acid compounds, such as 1,2-bis (methacryloylthio) ethane, Bis (2-acryloylthioethyl) ether and 1,4-bis (methacryloylthiomethyl) benzene; and aromatic vinyl compounds such as divinylbenzene, styrene, chlorostyrene, α-methylstyrene, α-methylstyrene dimer, Vinylnaphthalene, isopropenylnaphthalene and bromostyrene.

These copolymerizable monomers as a single product or in the form of a mixed product can be used from two or more species. The mixing ratio can be determined appropriately according to the purpose of use. In general, however, the copolymerizable monomers in an amount of 0.5 to 80 parts by weight per 100 parts by weight total monomers (Note: sum of polyfunctional (meth) acrylate monomers and the copolymerizable monomer further comprising a polymerizable Epoxy compound (described below), if these is used as an epoxy compound; hereinafter simply referred to as "total monomers") photochromic according to the invention polymerizable composition blended. If the mixing proportion the copolymerizable monomers 0.5 to 30 parts by weight per 100 Parts by weight of the total monomers, the resulting photochromic Material improved heat resistance on, which is particularly desirable.

Component (b)

Hereinafter, a chromene compound which is the component (b) in FIG the photochromic polymerizable composition of the present invention.

The used according to the invention Chromene compound is represented by the above general formula (I) represents.

According to the invention the chromene compound is a substituted or unsubstituted amino group on Benzochromenring or at a substituent, which with the Benzochromenring is connected.

The Chromene compound which is component (b) the aforesaid Problem of initial color when mixing with the aforementioned polyfunctional (Meth) acrylate monomers is polymerized and cured without the compound (Component (c)) is added, which in their molecules a Having epoxy group. According to the invention therefore component (b) and component (c) may be used in combination.

wobei R19 und R20 gleich oder verschieden sein können und Wasserstoffatome, substituierte oder unsubstituierte Alkylgruppen mit 1 bis 10 Kohlenstoffatomen oder substituierte oder unsubstituierte aromatische Kohlenwasserstoffgruppen mit 6 bis 10 Kohlenstoffatomen oder heterocyclische Gruppen bedeuten,
oder bei R16 handelt es sich um eine stickstoffhaltige heterocyclische Gruppe mit einem Stickstoffatom als Heteroatom, das an den Benzochromenring gebunden ist.In the chromene compound of the formula (II), the group R16 is a substituted or unsubstituted amino group of the formula

where R 19 and R 20 may be identical or different and denote hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms or substituted or unsubstituted aromatic hydrocarbon groups having 6 to 10 carbon atoms or heterocyclic groups,
or R16 is a nitrogen-containing heterocyclic group having a nitrogen atom as a heteroatom attached to the benzochromene ring.

When Substituents R19 and R20 for the substituted or unsubstituted amino group of the above Formula can known groups, such as hydrogen atoms, substituted or unsubstituted Alkyl groups with 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbons having 6 to 10 carbon atoms or heterocyclic rings, without limitations. Preferably however, are alkyl groups, benzene rings or naphthalene rings with 1 to 4 carbon atoms used. The substituents R19 and R20 can be the same or different. Specific examples of the amino group of the above formula include the methylamino group, ethylamino group, Propylamino group, isopropylamino group, dimethylamino group, diethylamino group, Dipropylamino group, methylethylamino group, 2-hydroxyethylamino group, Di (hydroxyethyl) amino group, di (cyanomethyl) amino group and Diphenylamino.

It it is desirable that the nitrogen-containing heterocyclic group, as the heteroatom, a nitrogen atom bound to the benzo-ring ring has 2 to 10 carbon atoms and preferably 2 to 6 carbon atoms to form the heterocyclic group. The heterocyclic Group can next to the nitrogen atom attached to the benzochromic ring is bound to contain a heteroatom. Preferably, it can Contain oxygen atom, a sulfur atom or a nitrogen atom, without a limitation consists of the heteroatom. As an aromatic hydrocarbon ring or aromatic heterocyclic ring attached to the heterocyclic Group are bound, can be mentioned, for example: a aromatic hydrocarbon ring of 6 to 10 carbon atoms and an aromatic heterocyclic ring, such as a benzene ring, a thiophene ring and a furan ring. As substituted or unsubstituted heterocyclic ring having a nitrogen atom as a hetero atom, the is bound to the benzochrome ring, or as a fused heterocyclic Ring in which the heterocyclic group is replaced with an aromatic Hydrocarbon ring or an aromatic heterocyclic ring For example, the pyrrolidinyl group, Piperidino group, hexamethyleneimino group, 2,2,6-6-tetramethylpiperidino group, Morpholino group, 2,6-dimethylmorpholino group, N-methylpiperadinyl group, Thiomorpholino group, indolyl group, 2-methylindolyl group, tetrahydroquinolyl group and aziridinyl group.

Further may be a known substituent on R16, z. An alkyl group, Aralkyl group, alkoxy group, trifluoromethoxy group, acyl group, Alkoxycarbonyl group, cyano group, aryl group, acyloxy group, nitro group, Hydroxy group or halogen atom.

below become the aforementioned ones Substituents described.

Although no special restrictions consist, the aforementioned Alkyl group generally 1 to 10 carbon atoms and in particular 1 to 4 carbon atoms, with respect to a simple Synthesis. Specific examples of the alkyl group include Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Although no special restrictions consist, the aforementioned Aralkyl group generally 7 to 16 carbon atoms and in particular 7 to 10 carbon atoms, with respect to a simple Synthesis. Specific examples of the aralkyl group include Benzyl group, phenylethyl group, phenylpropyl group and phenylbutyl group.

Although no special restrictions exist, the aforementioned alkoxy group in general to a substituted or unsubstituted alkyl group with 1 to 10 carbon atoms, a substituted or unsubstituted aryl group with 6 to 10 carbon atoms or around a hetero ring. To concrete Examples of include the alkoxy group the methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, tert-butoxy group, phenoxy group and naphthoxy group.

Although no special restrictions consist, the aforementioned Acyl group generally 2 to 15 carbon atoms and in particular 2 to 7 carbon atoms, with a view to a simple Synthesis. Specific examples of the acyl group include the Methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, Isopropylcarbonyl group, n-butylcarbonyl group and tert-butylcarbonyl group.

Although no special restrictions consist, the aforementioned Alkoxycarbonyl group generally 2 to 15 carbon atoms and in particular 2 to 7 carbon atoms, with regard to the simple synthesis. Specific examples of the acyl group include the Methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, Isopropoxycarbonyl group, n-butoxycarbonyl group and isobutoxycarbonyl group.

Although no special restrictions consist, the aforementioned Aryl group generally 6 to 20 carbon atoms and in particular 6 to 14 carbon atoms, with respect to a simple Synthesis. Specific examples of the aryl group include the Phenyl group, naphthyl group and tolyl group.

Although no special restrictions consist, the aforementioned Acyloxygruppe generally 1 to 15 carbon atoms, and preferably 2 to 7 carbon atoms, with respect to. a simple one Synthesis. Specific examples of the acyloxy group include Acetoxy group, propionyloxy group, benzoyloxy group and (meth) acryloyloxy group.

Although no special restrictions exist to concrete examples for the aforesaid Halogen atom, which is favorably in of the present invention, the fluorine atom, chlorine atom and bromine atom.

Although no special restrictions regarding the positions of the substituents and the number of Substituents exist at R16, it is desirable that the total number the substituent is generally not more than 3 and preferably not more than 2, for a simple synthesis.

In the aforesaid general formula (I) R17 and R18 are substituted or unsubstituted alkyl groups, substituted or unsubstituted ones Aryl groups or substituted or unsubstituted aromatic heterocyclic groups, wherein R17 and R18 are different from each other could and further together may form a ring.

When the aforementioned Alkyl group may be a known group without any limitations be used. Preferably, the alkyl group is but a group of 1 to 10 carbon atoms, and preferably with 1 to 6 carbon atoms. Specific examples of the alkyl group belong the Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, tert-butyl group and cyclohexyl group.

When aforementioned Aryl group may be a known group without any limitations be used. Preferably, however, an aryl group with 6 used up to 10 carbon atoms. Specific examples of the aryl group belong the phenyl group, tolyl group, xylyl group and naphthyl group.

When the aforementioned aromatic heterocyclic group can be a known group without any restrictions be used. Preferably, however, an aromatic heterocyclic Group with 2 to 12 carbon atoms and one nitrogen atom, Sulfur atom, or oxygen atom used as a heteroatom. To concrete Examples of the aromatic heterocyclic group include the furyl group, benzofuryl group, cyclic dibenzofurane group, thienyl group, benzothienyl group, cyclic dibenzothiophene group, N-methylpyrrolyl group, indolyl group, Pyridinyl group, quinolyl group, isoquinolyl group and N-methylcarbazole group.

When Ring, which is formed by bonding of R17 and R18, can be a norbornane ring, a bicyclo [3.3.1] 9-nonan ring and a Mention adamantane ring in addition to the rings formed by bonding the aforementioned alkyl groups, Aryl groups or aromatic heterocyclic groups formed have been.

The Alkyl groups, aryl groups and aromatic heterocyclic groups, which are represented by R17 and R18 may have a known substituent exhibit. Preferred examples of the substituent include Alkyl group, alkoxy group, aralkyl group, aryl group, acyl group, Alkoxycarbonyl group, substituted or unsubstituted amino group, Acyloxy group, nitro group, hydroxy group, cyano group and a halogen atom. These substituents can be the same with the substituents in the aforementioned group R16. Although no special restrictions in terms of the number of substituents, it is desirable the number is generally 0 to 4 and preferably 0 to 3 is, for a simple synthesis.

In the chromium composition according to the invention in concrete examples of the chromene compound, the Formula (I) for the following products:

• 1) 6-morpholino-3,3-bis (3-fluoro-4-methoxyphenyl) -3H-benzo (f) chromene;
• 2) 6-morpholino-3- (4-methoxyphenyl) -3- (4-trifluoromethoxyphenyl) -3H-benzo (f) chromene;
• 3) 6-piperidino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromene;
• 4) 6-piperidino-3-methyl-3-phenyl-3H-benzo (f) chromene;
• 5) 6-morpholino-3,3-bis (4-methoxyphenyl) -3H-benzo (f) chromene;
• 6) 6-hexamethyleneimino-3-methyl-3- (4-methoxyphenyl) -3H-benzo (f) -chromene;
• 7) 6-morpholino-3- (2-furyl) -3-methyl-3H-benzo (f) chromene;
• 8) 6-morpholino-3- (2-thienyl) -3-methyl-3H-benzo (f) chromene;
• 9) 6-morpholino-3- (2-benzofuryl) -3-methyl-3H-benzo (f) chromene;
• 10) 6-indolino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromene;
• 11) 3- (2-benzothienyl) -3-methyl-6-morpholino-3H-benzo (f) chromene; and
• 12) 6-hexamethyleneimino-3-methyl-3- (4-morpholinophenyl) -3H-benzo (f) chromene.

The Chromene compounds of the formula (I) may be in the form of a single Compound or used in a mixture of two or more compounds depending on the purpose.

Regarding the admixed amount of the chromene compounds of the formula (I) in the photochromic invention polymerizable composition are not particularly limited. The amount may be appropriate depending on the purpose be determined. If, for example, the photochromic polymerizable composition for optical lenses, such as spectacle lenses, is used, the chromene compound is generally in one Amount of 0.001 to 10 parts by weight per 100 parts by weight of blended throughout the monomers.

in the Generally, the color density of the cured product varies by hardening the photochromic invention polymerizable composition has been obtained, in some Scope in proportion to the admixed amount. If the chromene compound is in excess amounts However, the color density is no longer increasing in proportion to but the stability of the photochromism is impaired. Therefore, amounts the blended amount of the chromene compound is 0.01 to 5 parts by weight and preferably 0.01 to 1 part by weight per 100 parts by weight of the total monomers.

Component (c)

below becomes the epoxy compound which is the component (c) in the photochromic invention polymerizable composition is described.

According to the invention, any known epoxy compounds are used without limitations, provided that at least one or more epoxy groups are present in the molecules. For example, a reaction product of an epichlorohydrin with an alcoholic hydroxyl group-containing compound of a monohydric, dihydric or trihydric alcohol or with a a phenolic hydroxyl group-containing compound such as phenol or hydroquinone, and a reaction product of an epichlorohydrin with a carboxylic acid, like benzoic acid or terephthalic acid, be used.

It is according to the invention however, desirably, an epoxy compound having at least one or more unsaturated Double bonds in the molecules for the following reasons. If indeed one Epoxy compound having at least one or more unsaturated Double bonds in the molecules is used, the epoxy compound is fixed to the matrix, by copolymerization with another monomer, such as the polyfunctional (meth) acrylate monomer at the time of polymerization and hardening the photochromic polymerizable invention Composition, with only a minor impairment the property of the obtained cured product comes.

When example for the unsaturated one Double bond in the epoxy compound can be a vinyl group, a Mention allyl group and a (meth) acryloyl group. To favorable photochromic properties However, it is desirable to achieve the (meth) acryloyl group to use.

wobei A einen Rest einer eine alkoholische Hydroxylgruppe enthaltenden Verbindung mit einem Wert d, den Rest einer eine phenolische Hydroxylgruppe enthaltenden Verbindung mit einem Wert d oder einen Rest einer Carbonsäure mit einem Wert d bedeutet, R22 ein Wasserstoffatom oder eine Methylgruppe bedeutet und d eine ganze Zahl mit einem Wert von 1 bis 4 bedeutet.Among the epoxy compounds which can be used in the present invention, a preferred epoxy compound having no unsaturated double bond in the molecules is a compound represented by the following formula

wherein A represents a residue of an alcoholic hydroxyl group-containing compound having a value d, the residue of a phenolic hydroxyl group-containing compound having a value d, or a residue of a carboxylic acid having a value d, R22 represents a hydrogen atom or a methyl group, and d represents an integer with a value of 1 to 4 means.

In the aforesaid Formula which represents the epoxy compound having no unsaturated double bond has d is 1 or 2, and if d is 1, A is a Alkyl group which may be substituted with a hydroxyl group and 2 to 20 carbon atoms, a group of the formula - (OR) e -OH (where R is an alkylene group of 2 to 4 carbon atoms and e is an integer from 1 to 20), a cycloalkyl group substituted with a hydroxyl group and having from 6 to 7 carbon atoms, a phenyl group, which may be substituted by a hydroxyl group, or a benzoyl group, which may be substituted with a carboxyl group and, if d has the value 2, A represents an alkylene group containing a hydroxyl group may be substituted and has 2 to 20 carbon atoms, one Group of formula - (OR) e- (where R is an alkylene group containing 2 to 4 carbon atoms and e is an integer having a value from 1 to 20), a cycloalkylene group having a hydroxyl group may be substituted and has 6 to 7 carbon atoms, one Phenylene group which may be substituted with a hydroxyl group, a phthaloyl group, an isophthaloyl group, a terephthaloyl group or a group of the following formula

To concrete examples for the connection of the aforementioned Formula include Ethylene glycol glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, Diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, butyl glycidyl ether, Phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, a propylene oxide adduct of bisphenol A or a hydrogenated bisphenol A, Glycidyl terephthalate esters, spiroglycoldiglycidyl ethers and hydroquinone diglycidyl ethers.

wobei R23 und R26 unabhängig voneinander Wasserstoffatome oder Methylgruppen bedeuten, R24 und R25 gleich oder verschieden sind und Alkylengruppen bedeuten, die mit einer Hydroxylgruppe substituiert sein können und 1 bis 4 Kohlenstoffatome aufweisen, oder Gruppen der folgenden Formel bedeuten

und f und g unabhängig voneinander den Wert 0 oder 1 haben.Among the epoxy compounds, an epoxy compound having one or more unsaturated double bonds in the molecules, which can be particularly preferably used in the present invention, is represented by the following formula

wherein R23 and R26 independently represent hydrogen atoms or methyl groups, R24 and R25 are the same or different and are alkylene groups which may be substituted with one hydroxyl group and have 1 to 4 carbon atoms, or groups of the following formula

and f and g independently of one another have the value 0 or 1.

To Examples of the alkylene group in the above R29 and R25 Formula belong to one Methylene group, ethylene group, propylene group, isopropylene group, Butylene group, isobutylene group, trimethylene group and tetramethylene group. These groups can be substituted with a hydroxyl group.

To concrete examples of the compound used as a link with at least one epoxy group and a free-radically polymerizable Group in the molecules can be used belong Acrylic ester compounds and methacrylic ester compounds such as glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, Bisphenol A monoglycidyl ether (meth) acrylate, 4-glycidyloxybutyl (meth) acrylate, 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl (meth) acrylate, 3- (glycidyloxy-2-isopropyloxy) -2-hydroxypropyl (meth) acrylate and 3- (glycidyloxy-2-hydroxypropyloxy) -2-hydroxypropyl (meth) acrylate. Of these, glycidyl (meth) acrylate is preferable in view of on the resistance the photochromic effect.

The blended amount of the epoxy compound in the photochromic polymerizable composition of the present invention may be suitably determined depending on the kinds and blending proportions of the polyfunctional (meth) acrylate monomer and the chromene compound used and the kind of the epoxy compound used. When a polyfunctional (meth) acrylate monomer, which is commercially available, is used, the epoxy compound is used in an amount of not less than 1 part by weight, and preferably from 1 to 30 parts by weight per 100 parts by weight of the total monomers, irrespective of the amounts of the chromene compound and the Epoxy compound used, thereby avoiding the problem of the initial color and achieving the durability of photochromism to a practical extent. However, when an epoxy compound having no unsaturated double bond is used, curing tends to be delayed if its amount is too large. When a Epoxy compound should be used without unsaturated double bond, therefore, the amount thereof is 1 to 10 parts by weight and preferably 1 to 5 parts by weight per 100 parts by weight of the total monomers.

The thus obtained photochromic polymerizable composition can be polymerized and cured depending on the purpose.

Component (d)

below becomes the polymerization initiator (polymerization initiator) at it is the component (d) in the photochromic invention polymerizable composition is described.

It can any known radical polymerization initiator as a polymerization initiator without restrictions be used. Too representative Examples include Diallyl peroxides, such as benzoyl peroxide, p-chlorobenzoyl peroxide, decanoyl peroxide, Lauroyl peroxide and acetyl peroxide; Peroxyesters, such as tert-butyl peroxy-2-ethylhexanate, tert-butylperoxyneodecanoate, Cumyl peroxyneodecanate, tert-butyl peroxybenzoate, tert-butyl peroxyisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; Percarbonates, such as diisopropyl peroxycarbonate and di-sec-butyl peroxydicarbonate; and azo compounds such as azobisisobutyronitrile and the like. As photopolymerization catalysts can Acetophenone compounds, such as 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl and 1- (9-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one; α-carbonyl compounds, such as 1,2-diphenylethanedione and methylphenyl glyoxylate; and acylphosphine oxide compounds, such as 2,6-dimethylbenzoyldiphenylphosphine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide and 2,6-dimethoxybenzoyldiphenylphosphine oxide be used. These polymerization initiators can be used alone or in the form of two or more compounds in any one relationship be used depending on the monomers used. Furthermore, the Wärmepolymerisationskatalysator and the photopolymerization catalyst is used in combination become. When the photopolymerization catalyst is used, may in combination therewith be a known polymerization promoter, like a tertiary Amine or the like can be used.

The Amount of the radical polymerization initiator varies depending on the polymerization conditions, the type of initiator and the composition of the radically polymerizable monomer and can not be finally determined be, is but generally 0.001 to 10 parts by weight, and preferably 0.01 to 5 parts by weight per 100 parts by weight of the total polymerizable Monomers.

Other components

The Photochromic according to the invention Polymerizable composition can improve the properties depending on the use of the photochromic material by polymerization and curing the polymerizable Composition has been obtained, and that in an area where the hardening not impaired becomes. For example, the chromene compound used in the present invention a yellow to purple hue. It is however permissible to Chromene compound along with other known photochromic compounds to use to obtain a photochromic composition, the a neutral hue, such as gray, amber, brown and the like, in general for the photochromic lenses is preferred. With regard to the There are no combinations with other photochromic compounds special restrictions, d. H. a known photochromic compound can be used z. An oxazine compound, a fulgimide compound and / or a known chromene compound (hereinafter also referred to as "other known Chromene compound ") in addition to the invention used Chromene compound can be used.

When Fulgimide compound and oxazine compound can be known compounds used, for example, in the following US patents described 4,882,438, 4,960,678, 5,130,058, 4,913,544 and EP-06 006 69.

wobei R27 eine Alkylgruppe bedeutet, die verzweigt sein kann, R28 und R29 Alkylgruppen bedeuten, die voneinander verschieden sein können, und R28 und R29 aneinander unter Bildung eines Cycloalkanrings gebunden sein können, R30 und R31 Alkylgruppen, Alkoxygruppen oder Halogenatome bedeuten, R32 ein Halogenatom, eine substituierte oder unsubstituierte heterocyclische Gruppe mit einem Stickstoffatom als Heteroatom, das an einen Benzochromenring gebunden ist, oder eine kondensierte heterocyclische Gruppe bedeutet, wobei die heterocyclische Gruppe mit einem aromatischen Kohlenwasserstoffring oder mit einem aromatischen heterocyclischen Ring kondensiert ist, h eine ganze Zahl mit einem Wert von 0 bis 2 bedeutet und die Anzahl der Substituenten R30 wiedergibt und i eine ganze Zahl mit einem Wert von 0 bis 2 bedeutet und die Anzahl der Substituenten R32 wiedergibt.As the oxazine compound, any known compounds having a spirooxazine skeleton and photochromic properties can be used without limitation, e.g. B. an oxazine compound of the following formula

wherein R27 is an alkyl group which may be branched, R28 and R29 are alkyl groups which may be different from each other, and R28 and R29 may be bonded to each other to form a cycloalkane ring, R30 and R31 are alkyl groups, alkoxy groups or halogen atoms, R32 is a halogen atom, a substituted or unsubstituted heterocyclic group having a nitrogen atom as a heteroatom bonded to a benzochromene ring, or a condensed heterocyclic group, wherein the heterocyclic group is condensed with an aromatic hydrocarbon ring or with an aromatic heterocyclic ring, h is an integer having a value from 0 to 2, and the number of substituents represents R30, and i represents an integer of 0 to 2, and the number of substituents represents R32.

Regarding the alkyl groups in the context of R27, R28 and R29 in the above There are no special restrictions on the formula. They may be alkyl groups be used with 1 to 5 carbon atoms, for. The methyl group, Ethyl group, isopropyl group, n-propyl group, n-butyl group, isobutyl group and neopentyl group. As examples of the cycloalkane ring formed by bonding of groups R28 and R29 the cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring and mention cycloheptane ring.

Regarding the alkoxy group in the context of R30 and R31 in the aforementioned formula There are no special restrictions. It can Alkoxy groups having 1 to 4 carbon atoms are used, such as Methoxy group, ethoxy group, n-propoxy group, n-butoxy group, isobutoxy group and tert-butoxy group.

Regarding the halogen atoms in the context of R30 and R31 in the aforementioned formula There are no special restrictions. It can For example, fluorine, chlorine or bromine atoms can be used.

Regarding the substituted or unsubstituted heterocyclic group in the context of R32 in the aforementioned Formula containing as a heteroatom a nitrogen atom, the is bound to a benzochrome ring, there are no special ones Restrictions. It can commonly used groups of 2 to 10 carbon atoms, the form the heterocyclic group can be used. The ring can besides the nitrogen atom bound to the benzochrome ring, additionally contain a heteroatom. Although no special restrictions The heteroatom may be an oxygen atom or a sulfur atom or a nitrogen atom. As examples of the aromatic hydrocarbon ring or the aromatic heterocyclic ring associated with the heterocyclic Group to form a condensed heterocyclic group condensed, can be an aromatic hydrocarbon ring and an aromatic heterocyclic ring having 6 to 10 carbon atoms mention, z. As a benzene ring, thiophene ring, furan ring and in particular a Benzene ring.

When Substituent for the heterocyclic group, which as heteroatom is a nitrogen atom, which is bound to the benzochromene ring, or for the condensed heterocyclic group in which the heterocyclic group has a aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed, any known substituents can be without restrictions use. However, in view of a simple synthesis Alkyl groups, such as a methyl group, ethyl group, isopropyl group, n-propyl group and tert-butyl group; Alkoxy groups, such as a methoxy group, ethoxy group, isopropoxy group, n-propoxy group and tert-butoxy group; and halogen atoms, such as a Fluorine atom, chlorine atom and bromine atom.

Concrete examples of the substituted or unsubstituted heterocyclic ring having a nitrogen atom as a heteroatom bonded to the benzochromic ring or concrete examples of the condensed heterocyclic group in which the heterocyclic group is condensed with the aromatic hydrocarbon ring or the aromatic heterocyclic ring, include the pyrrolidinyl group, Piperidino group, hexamethyleneimino group, 2,2,6,6-tetramethylpiperidino group, morpholino group, 2,6-dimethylmorpholino group, N-methylpiperadinyl group, thiomorpholino group, indolyl group, 2-methylindolyl group, tetrahydroquinolyl group and aziridinyl group.

• 1) 1',5'-Dimethyl-6'-fluor-6''-morpholinodispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H), 3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin;
• 2) 6'-Fluor-1'-methyl-8''-methoxy-6''-piperidinodispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin;
• 3) 6'-Fluor-6''-morpholino-1'-neopentyldispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin;
• 4) 5',7'-Difluor-1'-methyl-6''-morpholinodispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin;
• 5) 6'-Fluor-1'-(2-methyl)-propyl-6''-morpholinodispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,9)-oxazin;
• 6) 6''-Indolino-1',5'-dimethyl-6'-fluordispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin; und
• 7) 6'-Methyl-6'-fluor-1-(2-methyl)-propyldispiro-(cyclohexan-1,3'-(3H)-indol-2'-(2H),3''-(3H)-naphtho-(3,2-a)-(1,4)-oxazin.

Specific examples of the oxazine compound that can be advantageously used in the present invention include:

• 1) 1 ', 5'-dimethyl-6'-fluoro-6''- morpholinodispiro (cyclohexane-1,3' - (3H) -indole-2 '- (2H), 3''- (3H) - naphtho (3,2-a) - (1,4) -oxazine;
• 2) 6'-fluoro-1'-methyl-8 "-methoxy-6" -piperidinodispiro (cyclohexane-1,3 '- (3H) -indole-2' - (2H), 3 '' - ( 3H) naphtho (3,2-a) - (1,4) -oxazine;
• 3) 6'-fluoro-6 "-morpholino-1'-neopentyl-bis-spiro (cyclohexane-1,3 '- (3H) -indole-2' - (2H), 3 '' - (3H) -naphtho ( 3,2-a) - (1,4) -oxazine;
• 4) 5 ', 7'-Difluoro-1'-methyl-6 "-morpholinodispiro (cyclohexane-1,3' - (3H) -indole-2 '- (2H), 3''- (3H) - naphtho (3,2-a) - (1,4) -oxazine;
• 5) 6'-fluoro-1 '- (2-methyl) -propyl-6''- morpholinodispiro (cyclohexane-1,3' - (3H) -indole-2 '- (2H), 3''- ( 3H) -naphtho- (3,2-a) - (1,9) -oxazine;
• 6) 6 '' - indolino-1 ', 5'-dimethyl-6'-fluorodispiro (cyclohexane-1,3' - (3H) -indole-2 '- (2H), 3''- (3H) - naphtho (3,2-a) - (1,4) -oxazine; and
• 7) 6'-methyl-6'-fluoro-1- (2-methyl) -propyldispiro (cyclohexane-1,3 '- (3H) -indole-2' - (2H), 3 '' - (3H) naphtho (3,2-a) - (1,4) oxazine.

The aforementioned Oxazine compounds can as individual compounds or in a mixture of two or more species in any ratio be used.

wobei R33 eine Alkylgruppe, eine Cycloalkylgruppe, eine Arylgruppe oder eine Heteroarylgruppe bedeutet, R34 eine Cyanogruppe, eine Cyanomethylgruppe oder eine m-Cyanophenylgruppe bedeutet, R35 ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, die substituiert sein kann, oder ein Halogenatom bedeutet, X ein Schwefelatom oder ein Sauerstoffatom bedeutet, j eine ganze Zahl mit einem Wert von 0 bis 2 entsprechend der Anzahl der Substituenten R35 bedeutet und, wenn j den Wert 2 hat, die Gruppen R35 voneinander verschieden sein können.As the aforementioned fulgimide compound of the present invention, any compounds having a fulgimide skeleton and photochromic properties can be used without limitation, e.g. For example, a fulgimide compound of the following formula

wherein R33 represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group, R34 represents a cyano group, a cyanomethyl group or an m-cyanophenyl group, R35 represents a hydrogen atom, an alkyl group, an aryl group which may be substituted, or a halogen atom, X. Represents sulfur or an oxygen atom, j represents an integer having a value of 0 to 2 corresponding to the number of substituents R35, and when j is 2, the groups R35 may be different from each other.

Although there are no special restrictions in terms of the alkyl groups in the context of R33 and R35 in the aforementioned general Formula gives, can Alkyl groups having 1 to 4 carbon atoms are used, such as the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group.

Regarding the cycloalkyl group in the scope of R33 in the aforementioned general Although there are no special restrictions, formulas can Cycloalkyl groups with 3 to 6 carbon atoms are used z. The cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group.

Although there are no particular restrictions on the aryl group of R33 in the aforementioned general formula, a phenyl group is generally used. Any known substituents for the aryl group can be used without limitations. Preferred examples include alkoxy groups such as the methoxy group and the ethoxy group; Alkyl groups having 1 to 4 carbon atoms, such as the methyl group, ethyl group, isopropyl group, n-butyl group and tert-butyl group; Halogen atoms such as a fluorine atom, chlorine atom and bromine atom; the cyano group; and the trifluoromethyl group. There are no particular restrictions on the number of substituents on the aryl group. However, in view of easy synthesis, the number of substituents is 0 to 3, and preferably 0 to 2.

Although with regard to the heteroaryl group in the context of R33 in the abovementioned general Formula no special restrictions are generally considered to be such heteroaryl groups for example, a thiophene ring, a furan ring, a benzothiophene ring and a benzofuran ring used. As a substituent for the heteroaryl group can known substituents are used without limitations. To Examples of this belong Alkoxy groups such as the methoxy group and ethoxy group; With alkyl groups 1 to 4 carbon atoms, such as the methyl group, ethyl group, isopropyl group, n-butyl group and tert-butyl group; Halogen atoms, such as a fluorine atom, Chlorine atom and bromine atom; the cyano group; and the trifluoroethyl group. With regard to the number of substituents on the aryl group there there are no special restrictions. However, in terms of ease of synthesis, the number of substituents is 0 to 3 and preferably 0 to 2.

Although with regard to the aryl group in the context of R35 in the abovementioned general Formula no special restrictions In general, a phenyl group can be used. Any known substituents for the aryl group can be used without limitations be used. Preferred examples include alkoxy groups such as Methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, Isobutoxy group and tert-butoxy group; Alkyl groups with 1 to 4 Carbon atoms, such as the methyl group, ethyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group; Halogen atoms, such as a fluorine atom, chlorine atom and bromine atom; the cyano group; and the trifluoromethyl group. With regard to the number of substituents There are no special restrictions on the aryl group. For ease of synthesis, the number of substituents is but 0 to 3 and preferably 0 to 2.

• 1) N-Cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 2) N-Cyanomethyl-6,7-dihydro-2-(4'-methoxyphenyl)-4-methylspiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 3) N-Cyano-6,7-dihydro-4-methyl-2-phenylspiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 4) N-Cyano-6,7-dihydro-4-methylspiro-(5,6-benzo[b]furandicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 5) N-Cyano-4-cyclopropyl-6,7-dihydrospiro-(5,6-benzo[b]furandicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 6) N-Cyano-6,7-dihydro-4-methylspiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 7) N-Cyanomethyl-9-cyclopropyl-6,7-dihydrospiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 8) N-Cyanomethyl-9-cyclopropyl-6,7-dihydro-2-(4'-methoxyphenylspiro-(5,6-benzo[b]thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan);
• 9) N-Cyanomethyl-4-cyclopropyl-6,7-dihydro-2-phenylspiro-(5,6-benzo[b)thiophendicarboxyimid-7,2-tricyclo[3.3.1.1^3,7]decan); und
• 10) N-(3'-Cyanophenyl)-6,7-dihydro-4-methyl-2-(4'-methoxyphenyl)-spirobenzothiophencarboxyimid-7,2'-tricyclo[3.3.1.1^3,7]decan.

Specific examples of the fulgimide compound used according to the invention advantageously include the following compounds:

• 1) N -cyanomethyl-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 2) N -cyanomethyl-6,7-dihydro-2- (4'-methoxyphenyl) -4-methylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane );
• 3) N-cyano-6,7-dihydro-4-methyl-2-phenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 4) N-cyano-6,7-dihydro-4-methylspiro (5,6-benzo [b] furandicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 5) N-cyano-4-cyclopropyl-6,7-dihydrospiro (5,6-benzo [b] furandicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 6) N -cyano-6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 7) N -cyanomethyl-9-cyclopropyl-6,7-dihydrospiro- (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• 8) N -cyanomethyl-9-cyclopropyl-6,7-dihydro-2- (4'-methoxyphenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane) ;
• 9) N -cyanomethyl-4-cyclopropyl-6,7-dihydro-2-phenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane); and
• 10) N- (3'-Cyanophenyl) -6,7-dihydro-4-methyl-2- (4'-methoxyphenyl) -spirobenzothiophenecarboximide-7,2'-tricyclo [3.3.1.1 ^3,7 ] decane.

The aforementioned Fulgimide compounds can individually or in a mixture of two or more compounds in any conditions be used.

In addition to the invention used Chromium compound can any other chromene compounds with a photochromic nature be used.

According to the invention, the mixing ratios of the oxazine compounds, fulgimide compounds and other known chromene compounds are not particularly limited, but these ratios can be properly determined by taking into consideration the properties of the photochromic compounds. When the oxazine compounds, fulgimide compounds and / or other known chromene compounds are to be added to the photochromic polymerizable composition of the present invention, the addition amount is usually 0.001 to 10 parts by weight, and preferably 0.01 to 1 Part by weight per 100 parts by weight of the total monomers.

Further may be a UV stabilizer of the photochromic polymerizable invention Composition can be added. By adding the UV stabilizer can be the photochromic resistance continues improve. When the fulgimide compound is used in combination In particular, the light fastness is improved. When trying is a neutral hue using the oxazine compound and To achieve the Fulgimidverbindung in combination, it is possible, a over time occurring change of the neutral hue to prevent.

One known UV stabilizer can be used without restrictions, for. B. a photostabilizer based on a sterically hindered Amines, a photostabilizer based on a sterically hindered Phenol, a sulfur-type antioxidant, and a photostabilizer of the phosphoric ester type.

Regarding the amount of UV stabilizer used are not specific Restrictions. Usually is however, the amount used is 0.01 to 5 parts by weight, and preferably 0.02 to 1 part by weight per 100 parts by weight of the total monomers.

if necessary can Furthermore, various additives are added, for. As a UV absorber Benzotriazole type or a UV absorber Benzophenone type, an antioxidant, a means of prevention of discoloration, an antistatic equipment Agent, a phosphorescent dye, a pigment and a perfume.

polymerization and curing the polymerizable composition

below is a process for the preparation of the photochromic invention Material by polymerization and curing of the photochromic invention polymerizable composition.

According to the invention with regard to the polymerization process for the preparation of a Polymers of the photochromic polymerizable composition no restrictions. It can Any radical polymerization can be used. The polymerization is carried out using free-radical polymerization initiators, such as various peroxides and azo compounds, or by irradiation with UV rays, α rays, β rays or γ-rays, or achieved using both methods. A representative Polymerization process is a cast polymerization in which the Photochromic according to the invention polymerizable composition containing a radical polymerization initiator contains, in a mold made by an elastomeric seal or spacer is worn, in a heating furnace or by irradiation is polymerized with UV rays or visible light and then removed becomes.

What As regards the polymerization conditions, the polymerization temperature varies depending on the type of the polymerizable monomer and the radical Polymerization initiator and leaves not final establish. In general, however, the polymerization starts at a relatively low temperature. The temperature is then gradually increased and on End of the polymerization becomes the photochromic polymerizable composition hardened, resulting in the so-called "conical" two-stage polymerization results. Like the temperature, so does the polymerization time dependent on of different factors. It is desirable, an optimal Set time according to the conditions. In general it is however, desirable that the polymerization within 2 to 40 hours is over.

Photochromic material

The thus obtained photochromic material of the invention also in the form of a polymer favorable photochromic properties. The polymer can be advantageously Way for Applications such as photochromic glasses and photochromic lenses, be used.

The Photochromic according to the invention Material can be used within a wide range of applications be, for. For example a variety of storage materials for the replacement of photosensitive Silver salt materials, for Copying materials, photosensitive materials for printing, Storage materials for Cathode ray tubes, photosensitive materials for Laser beams and photosensitive materials for holography. The photochromic invention Material can also be used for photochromic lenses, optical fibers, as display material, as actinometer and for be used for decorative purposes.

For example can for photochromic lenses without restrictions a method that allows a uniform dimming nature to achieve. In concrete terms, a method can be used in which a polymer film, in which the photochromic material according to the invention is homogeneously distributed, sandwiched in the lens, and a method in which the chromene compound of the present invention is polymerizable in the aforementioned Dispersed monomers and polymerized by a given method becomes.

Examples

below For example, the present invention will be described in detail by way of examples. However, these examples are not intended to limit the invention in any way.

below become the abbreviations for connections, used in Examples and Comparative Examples be explained.

1. Epoxy compounds

• GMA: glycidyl methacrylate
• GA: glycidyl acrylate
• MGMA: β-methylglycidyl methacrylate
• MGR: β-methylglycidyl acrylate
• BPMGMA: bisphenol A monoglycidyl ether methacrylate
• GBMA: 4-glycidyloxybutyl methacrylate
• GEHPMA: 3- (glycidyl-2-oxyethoxy) -2-hydroxypropyl methacrylate
• GIHPA: 3- (glycidyloxy-1-isopropyloxy) -2-hydroxypropyl acrylate
• EGGE: ethylene glycol glycidyl ether
• PGGE: propylene glycol glycidyl ether
• FDGE: terephthalic acid diglycidyl ether
• BGE: butyl glycidyl ether
• HDGE: 1,6-hexanediol glycidyl ether

2. Polyfunctional (meth) acrylate monomers

• 3G: triethylene glycol dimethacrylate (trade name: NK Ester 3G, product of the company Shin-Nakamura Kagaku Co.)
• 4G: tetraethylene glycol dimethacrylate (trade name: NK Ester 4G, product of the company Shin-Nakamura Kagaku Co.)
• 3PG: tripropylene glycol dimethacrylate (trade name: NK Ester 3PG, product of the company Shin-Nakamura Kagaku Co.)
• BP-2EM: 2,2-bis- (9-methacryloyloxypolyethoxyphenyl) -propane (in Mixture with an average number of moles of ethylene oxide chains of 2.2) (trade name: Light Ester BP-2EM, product of Fa. Kyoeisha Kagaku Co.)
• BR-MA: 2,2-bis- (3,5-dibromo-4-methacryloyloxyethoxyphenyl) -propane (trade name: Light Ester BR-MA, product of the company Kyoeisha Kagaku Co.)
• TEGDMA: triethylene glycol dimethacrylate (trade name: TEGDMA, Product of the company Mitsubishi Gas Kagaku Co.)
• 3EG: triethylene glycol dimethacrylate (trade name: Light Ester 3EG, product of the company Kyoeisha Kagaku Co.)
• PRO-631: 2,2-bis- (4-methacryloyloxypolyethoxyphenyl) -propane (Trade name: PRO-631, product of the company Sertomar Co.)

3. Copolymerizable monomers

• MMA: methyl methacrylate
• MS: α-methylstyrene
• MSD: α-methylstyrene dimer
• BzMA: benzyl methacrylate
• HEMA: 2-hydroxyethyl methacrylate

4. Radical polymerization initiator

• Perbutyl ND: tert-butyl peroxyneodecanate (trade name: Perbutyl ND, product of Nippon Yushi Co.)

5. chromene compounds

• C1) 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino-3H-benzo (f) -chromene;
• C2) 3,3-bis (4-methoxyphenyl) -6-morpholino-3H-benzo (f) -chromene;
• C3) 3- (4-methoxyphenyl) -3- (3-trifluoromethyl-4-methoxyphenyl) -6-piperidino-3H-benzo (f) -chromene;
• C4) 3,3-bis (4-methoxyphenyl) -6-N-methylpiperadino-3H-benzo (f) -chromene;
• C5) 3- (2-furyl) -3-methyl-6-morpholino-3H-benzo (f) -chromene;
• C6) 3-methyl-3- (2-naphthyl) -6-morpholino-3H-benzo (f) -chromene;
• C8) 6-morpholinospiro- (fluoren-9,3'-3H-benzo (f) -chromene);
• C9) 6-indolino-3-methyl-3- (2-naphthyl) -3H-benzo (f) -chromene;
• C10) 3- (2-Benzofuryl) -3-methyl-6-morpholino-3H-benzo (f) -chromene;
• C11) 6-hexamethyleneimino-3-methyl-3- (4-morpholinophenyl) -3H-benzo (f) -chromene;

below become the structural formulas for the aforementioned ones Chromene compounds (C1 to C11) indicated.

6. Fulgimide compounds

• F1) N -cyanomethyl-4-methyl-6,7-dihydro-2-phenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane);
• F2) N -cyanomethyl-4-methyl-6,7-dihydro-2- (4'-methoxyphenylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo [3.3.1.1 ^3,7 ] decane) ; and
• F3) N -cyanomethyl-6,7-dihydro-4-methylspiro (5,6-benzo [b] thiophenedicarboxyimide-7,2-tricyclo (3.3.1.1 ^3,7 ) decane).

7. oxazine compounds

• SP1) 6'-fluoro-1'-methyl-8 "-methoxy-6" -morpholinodispiro (cyclohexane-1,3 '- (3H) -indole-2' - (2H), 3 '' - ( 3H) naphtho (3,2-a) - (1,4) -oxazine;
• SP2) 6'-fluoro-1 ', 5'-dimethyl-6 "-morpholinodispiro (cyclohexane-1,3' - (3H) -indole-2 '- (2H), 3' '- (3H) - naphtho (3,2-a) - (1,4) -oxazine;
• SP3) 6'-fluoro-1'-isobutyl-6'-morpholinodispiro (cyclohexane-1,3 '- (3H) -indole-2' - (2H), 3 '' - (3H) -naphtho- (3 , 2-a) - (1,4) -oxazine; and
• SP4) 3 ', 3'-dimethyl-1'-isobutylspiro (3H) -indole-2' - (2H), 3 "- (3H) -naphtho- (3,2-a) - (1,4 ) oxazine).

below become the structural formulas for the aforementioned ones Fulgimide compounds (F1 to F3) and the oxazine compounds (SP1 to SP4).

Example 1 (comparison)

90 Parts by weight "3G" at which it is a polyfunctional (meth) acrylate monomer and 10 parts by weight of the epoxy compound "GMA" mixed at room temperature and stirred for 2 hours. In this solvent mixture were stirred 0.05 parts by weight of the chromene compound "C1" and 1 part by weight of perbutyl ND brought as a polymerization initiator in solution. After dissolution the chromene compound gave almost no change in the solution mixture. The solution mixture was in a shape consisting of a glass plate and a seal composed of an ethylene / vinyl acetate copolymer, cast and the casting polymerization subjected. The polymerization was carried out using a hot air oven under gradual increase the temperature from 30 to 90 ° C within a period of 18 hours and with 2 hours retention the temperature of 90 ° C carried out. After the polymerization, the polymer was taken out of the glass mold.

• ➀ Maximale Absorptionswellenlänge (λmax): Nach Entwicklung des Farbtons wird λmax des Polymeren unter Verwendung eines Spektrophotometers (Sofort-Mehrkanal-Photodetektor MCPD 1000) der Fa. Otsuka Denshi Kogyo Co. festgestellt.
• ➁ Farbdichte (T0) = ε (120) – ε (0)
• ➂ (120): Absorption des Polymeren bei der maximalen Absorptionswellenlänge nach einer Bestrahlungszeit von 120 Sekunden unter den vorerwähnten Bedingungen.
• ➃ Anfängliche Farbe ε (0): Absorption des Polymeren bei der Wellenlänge, die der maximalen Absorptionswellenlänge bei Bestrahlung mit Licht entspricht, unter strahlungsfreien Bedingungen.

Using the xenon lamp L-2480 (300 W) SHL-100 (product of Hamamatsu Photonics Co.), the obtained polymer (thickness 2 mm) was irradiated with an intensity of 365 nm = 2.4 mW / cm ² and 245 nm = 24 μW / cm ² on the surface of the polymer through an Aeromas filter (product of the Corning Co.) irradiated for 120 seconds to measure the photochromic properties, referred to below be specified manner described.

• ➀ Maximum absorption wavelength (λmax): After development of hue, λmax of the polymer is detected by using a spectrophotometer (MCPD 1000 instantaneous multi-channel photodetector) of Otsuka Denshi Kogyo Co.
• ➁ color density (T0) = ε (120) - ε (0)
• ➂ (120): absorption of the polymer at the maximum absorption wavelength after an irradiation time of 120 seconds under the aforementioned conditions.
• ➃ Initial color ε (0): Absorption of the polymer at the wavelength corresponding to the maximum absorption wavelength upon irradiation with light, under radiation-free conditions.

The following test was performed to accelerate the aging. The measurement was carried out using a Xenon Fadometer (FA-25AX-HC) of Suga Shikenki Co. The light fastness was evaluated by the above-described method by causing the cured product to develop color by irradiating with light for 200 hours using the aforementioned xenon fadometer. The color density (T ₂₀₀ ) was determined from the absorption at the maximum absorption wavelength based on the color of the photochromic compound at that time. The color density was evaluated before and during aging. The initial color density (T0) and the color density (T ₂₀₀ ) after the aging accelerating test were measured. The light fastness is indicated as follows:

• Light fastness (%) = (T ₂₀₀ / T ₀ ) × 100

Examples 2 to 22

In Example 1 were the types and amounts of polyfunctional (Meth) acrylate monomers and the epoxy compounds as described changed in Table 1 or it became the procedure in the same way depending on the individual case as carried out in Example 1, but a copolymerizable monomer to form the cured products was added. The obtained cured products were on their consistency the photochromism and its initial staining by the same evaluation method as evaluated in Example 1. The results are shown in Table 1.

Examples 23 to 34

Hardened products were obtained as in Example 4 except that the chromene compound used as specified modified in Table 2 has been. The products were based on the permanence of photochromism and initial color rated. The results are shown in Table 2.

Examples 35 to 38

Hardened products were obtained by the same method as in Example 4, wherein but the types and quantities of the chromene compounds used as specified modified in Table 3 were. Further, oxazine compounds and fulgimide compounds added. The products were based on permanence of photochromism and initial color rated. The results are shown in Table 3.

Comparative Examples 1 to 7

polymerizable Compositions were prepared by adding 1 part by weight of perbutyl ND as a polymerization initiator to those listed in Table 4 Given compositions, followed by mixing and stirring, however, no epoxy compound was used. The obtained polymerizable compositions were the same processing as in Example 1 subjected. The obtained cured products were on resistance photochromism and initial staining evaluated in the same manner as in Example 1. The results are listed in Table 4.

The Hardened products obtained in Comparative Examples showed Compared to the cured ones Products of the examples a considerable initial coloration and also showed a significantly reduced resistance the photochromy. When no epoxy compound was added, it changed the hue of the developed color compared to the situation upon addition of an epoxy compound. Furthermore, the color changed in dependence on the type of monomer.

Claims (12)

A photochromic polymerizable composition comprising: (a) a polyfunctional (meth) acrylate monomer; (b) at least one chromene compound of the formula (I)

wherein R 16 is a substituted or unsubstituted amino group or a nitrogen-containing heterocyclic group having, as a heteroatom, a nitrogen atom bonded to a benzochrome ring, wherein R 17 and R 18 may be the same or different and are alkyl groups, aryl groups or aromatic heterocyclic groups may have a substituent, and wherein R 17 and R 18 may be bonded to each other to form a ring, and (c) a compound having at least one epoxy group therein, provided that the polyfunctional (meth) acrylate monomer is not only ethylene glycol diacrylate monomer , Diethylene glycol dimethacrylate monomer, triethylene glycol dimethacrylate monomer, tetraethylene glycol dimethacrylate monomer, ethylene glycol bis-glycidyl methacrylate monomer, bisphenol A dimethacrylate monomer, 2,2-bis (4-methacryloxyethoxyphenyl) propane monomer or 2,2-bis (3, 5-dibromo-4-methacryloxyethoxyphenyl) propane monomer or a mixture of T etraethylene glycol dimethacrylate and triethylene glycol dimethacrylate. Photochromic polymerizable composition according to Claim 1, further comprising (d) a polymerization initiator. Photochromic polymerizable composition according to Claim 1, wherein the compound having at least one or more Epoxy groups in the molecules, which represents the component (c), further at least one or has multiple (meth) acryloyl groups in the molecules. A photochromic polymerizable composition according to claim 1, wherein the compound having at least one or more epoxy groups in the molecules constituting the component (c) is the one represented by the following formula

wherein R 23 and R 26 are independently hydrogen atoms or methyl groups, R 29 and R 25 are alkylene groups having 1 to 4 carbon atoms which may be substituted with the same or different hydroxyl groups, or groups represented by the following formula

and wherein f and g, independently of one another, are 0 or 1. A photochromic polymerizable composition according to claim 1, containing the chromene compound which is the component (b) in an amount of 0.001 to 10 parts by weight per one unit of 100 parts by weight of the total monomers in the composition. Photochromic polymerizable composition according to Claim 1, containing the polyfunctional (meth) acrylate monomer (a) in an amount of 70 to 100 parts by weight and a compound with at least one or more epoxy groups in the molecules, the Component (c) is in an amount of 1 to 30 parts by weight. A photochromic material comprising a polymerizable Composition of claim 1. A composition according to claim 1, wherein in the compound of the formula (I) R 16 is a methylamino group, ethylamino group, propylamino group, Isopropylamino group, dimethylamino group, diethylamino group, dipropylamino group, Methylethylamino group, 2-hydroxyethylamino group, di (hydroxyethyl) amino group, Di (cyanomethyl) amino group, diphenylamino group, pyrrolidinyl group, Piperidino group, hexamethyleneimino group, 2,2,6,6-tetramethylpiperidino group, Morpholino group, 2,6-dimethylmorpholino group, N-methylpiperadinyl group, Thiomorpholino group, indolyl group, 2-methylindolyl group, tetrahydroquinolyl group or aziridinyl group. The composition of claim 1, wherein the substituted or unsubstituted amino group is represented by the formula -N (R19) R20 wherein R 19 and R 20 may be the same or different and represent hydrogen atoms, substituted or unsubstituted alkyl groups having 1 to 10 carbon atoms, substituted or unsubstituted aromatic hydrocarbon groups having 6 to 10 carbon atoms or heterocyclic groups. A composition according to claim 1, wherein the substituted or unsubstituted nitrogen-containing heterocyclic group at least one compound selected from the group consisting from a pyrrolidinyl group, piperidino group, hexamethyleneimino group, 2,2,6,6-tetramethylpiperidino group, morpholino group, 2,6-dimethylmorpholino group, N-methylpiperadinyl group, thiomorpholino group, indolyl group, 2-methylindolyl group, tetrahydroquinolyl group or aziridinyl group. A composition according to claim 1, wherein the chromene compound in (b) is at least one compound selected from the group consisting of (C1) 3,3-bis (3-fluoro-4-methoxyphenyl) -6-morpholino-3H-benzo (f) chromen; (C2) 3,3-bis (4-methoxyphenyl) -6-morpholino-3H-benzo (f) chromen; C3) 3- (4-methoxyphenyl) -3- (3-trifluoromethyl-4-methoxyphenyl) -6-piperidino-3H-benzo (f) chromen; (C4) 3,3-bis (4-methoxyphenyl) -6-N-methylpiperadino-3H-benzo (f) chromen; (C5) 3- (2-furyl) -3-methyl-6-morpholino-3H-benzo (f) chromene; (C6) 3-methyl-3- (2-naphthyl) -6-morpholino-3H-benzo (f) chromen; (C8) 6-morpholinospiro (fluorene-9,3'-3H-benzo (f) chromene; (C9) 6-indolino-3-methyl-3- (2-naphthyl) -3H-benzo (f) chromen; (C10) 3- (2-Benzofuryl) -3-methyl-6-morpholino-3H-benzo (f) chromen; and (C11) 6-hexamethyleneimino-3-methyl-3- (4-morpholinophenyl) -3H-benzo (f) chromene. Photochromic polymerizable composition according to Claim 1, wherein a polyfunctional (meth) acrylate monomer (a) at least one is selected is selected from the group consisting of propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, Tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Polybutylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 2,2-bis (4- (meth) acryloyloxy-polyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloyloxypolypropoxyphenyl) propane, ester compound from di (meth) acrylic acid with a hydrogenated bisphenol-A-ethylene oxide adduct, dimethylol tricyclodecane polyethoxydi (meth) acrylate, Trimethylolpropane tri (meth) acrylate, reaction product of bisphenol A-ethylene oxide or propylene oxide adduct with glycidyl (meth) acrylate, and reaction product hydrogenated bisphenol A-ethylene oxide or propylene oxide adduct with Glycidyl (meth) acrylate.